Vulcanization accelerator



Patented Dec. 31, 1940 VULCANIZATION ACCELERATQR Joy G. Lichty, Stow,Ohio, assignor to Wingfot Corporation, Wilmington, lDeL, a corporationof Delaware No Drawing. Application April .24, 1937, Serial No. 133,812

16 Claims.

This invention relates to the vulcanization of rubber. Moreparticularly, it relates to the acceleration of the vulcanization ofrubber by the use of the reaction products of aldehydes with 5 aminohydroxy propanes.

It is disclosed in copending application Serial No. 102,249 filedSeptember 23, 1936, that the amino hydroxy propanes, including certainsubstituted amino hydroxy propanes accelerate the vulcanization ofrubber. The present invention resides in the discovery that, if theseamino hydroxy propanes are reacted with .aldehydes, products are formedwhich are also good vulcanization accelerators.

The amino hydroxy propanes employed in the practice of the invention maybe prepared by reacting ammonia or certain amines with a halo- .genhydrin of propane corresponding to the product desired. For example,l-amino-Z, 3-dihydroxy propane may be prepared as follows:

A solution of grams of l-chloro-Z, S-dihydroxypropane and 40 grams ofsodium hydroxide in 400 cc. of water and 1010 grams of 28% aqueousammonium hydroxide was maintained at 1520 C. for five hours. The excessof ammonia and the water were then removed by distillation under reducedpressure. The residue was treated with methyl alcohol and filtered toremove the sodium chloride. Distillation of the filtrate gave 52.3 gramsof 1-amino-2, 3-dihydroxy propane boiling at -140" C. at two millimeterspressure. I There Was a 23 gram residue of condensed or polymerizedmaterial left from the distillation. Redistillation of the firstmentioned fraction gave a product boiling at The otheraminohydroxypropanes, such as diamino propanol (3), Z-amino-l,3-dihydroxy propane, l-amino Z-hydroxy propane, l-amino 3- hydroxypropane, etc., may be similarly prepared by substituting the properchlorhydrin or other halogen hydrin for the 1-chloro-2, B-dihydroxypropane of the example.

Also, if desired, the ammonia of the example may be replaced by aprimary aliphatic amine, which may be straight chain, branched chain, orcyclic, saturated or unsaturated, or aryl substituted, which arylsubstitution group may be either carbocyclic or heterocyclic.Representative of these amines are methyl amine, ethyl amine, the propylamines, the butyl amines, etc, the allyl amines, and other unsaturatedprimary aliphatic amines, benzyl amine, furfuryl amine, tetrahydrofurfuryl amine, cyclohexyl amine, ring substituted cyclohexylamines, andthe actetrahydronaphthylamines. Also included are the the primary polyamines, such as ethylene diamine, the poly-ethylene polyamines,propylene diarnine, cyclohexylene diamine, etc.

These amino hydroxy propanes react readily 5 with aldehydes to yieldcondensation products.

The aldehydes used may be saturated or unsaturated; alkyl, aryl oraralkyl; carbocyclic or heterocyclic; etc. Aldols and other aldehydecondensationmaterials may also be employed.

Included among these materials are formaldehyde, heptaldehyde,propionaldehyde, beta hydroxy naphthaldehyde, acetaldehyde,butyraldehyde, crotonaldehyde, benzaldehyde, furfuraldehyde, aldol,alpha methyl beta ethyl acrolein, 1 5 alpha ethyl beta propyl acrolein,etc.

Butyraldehyde may be reacted with l-amino-Z, 3-dihydroxy propane asfollows;

Fifteen grams of butyraldehyde were added in small portions to 18.9grams of 1-amino-2, 3- 20 dihy-droxy propane with stirring. The productwas finally heated to 125 C. to remove therwater. The yield wasquantitative.

Similarly, butyraldehyde may be reacted with diamino propanol-2 asfollows:

18.2 grams of butyraldehyde were added in small portions to 11.4 gramsof diamino propano1-2 with stirring. The product was heated to to removethe Water. The yield was quantitative.

Any other aldehyde or any of the otheramino propanols may be substitutedfor the substances of the preceding examples.

It will also be understood that it is not intended to limit the productsto the proportions of reactants used in the examples. Since there areseveral ways in which the ingredients might react including condensationof the aldehyde with itself, the proportions may be varied within 0 widelimits without exceeding the scope of the invention. For example, theproportion might be one mol of aldehyde to two mols of amines or one molof amine to almost any excess of aldehyde. In the latter case, it may bedesirable to 45 remove the excess aldehyde from the product.

Also, it is not intended that the invention shall be limited to the puresubstituted or unsubstituted amino propanols. It is pointed out in theaforementioned copending application No. 102,- 50 249, filed September23, 1936, that in some instances it may be desirable to employ therelatively crude products of the reaction of the halogen hydroxypropanes with the ammonia or amine directly as an accelerator.Similarly, these un- 55 Parts by weight Rubber (extracted pale crepe)100 Zinc oxide 5 Sulfur 3 Stearic acid 1.5 Accelerator 0.5

Representative materials of the invention were compounded with rubber inaccordance with the above formula, subjected to vulcanization andtested.

The typical test data follow.

Ult.

Tensile Cure in mins. Kgms/cm. Lgms/cm. elong. at r. figs 5,5 500% 700%in cen Condensate of butyraldehyde with l-amino-Z, 3-dihydroxy propaneCondensate of butyraldehyde with diamiuo propano1-2 From these data, itis seen that the materials possess very good accelerating properties.

Although only the preferred embodiment of the invention has beendescribed in detail, it will be apparent to those skilled in the artthat various modifications may be made therein without departing fromthe spirit of the invention or the scope of the appended claims. It isintended that the patent shall cover, by suitable expression in theappended claims, whatever features of patentable novelty reside in theinvention.

What I claim is:

1. The method of treating rubber which comprises vulcanizing the rubberin the presence of an aldehyde derivative of a primary amino hydroxypropane.

2. The method of treating rubber which comprises vulcanizing the rubberin the presence of an aldehyde derivative of a di (primary amino)hydroxy propane.

3. The method of treating rubber which comprises vulcanizing the rubberin the presence of an aldehyde derivative of a primary amino dihydroxypropane.

4. The method of treating rubber which comprises vulcanizing the rubberin the presence of the reaction product of an aliphatic aldehyde and aprimary amino hydroxy propane.

5. The method of treating rubber which comprises vulcanizing the rubberin the presence of the reaction product of an aromatic aldehyde and aprimary amino hydroxy propane.

.6. The method of treating rubber which comprises vulcanizing the rubberin the presence of the reaction product of butyraldehyde and 1- amino-2,3-dihydroxy propane.

7. The method of treating rubber which comprises vulcanizing the rubberin the presence of the reaction product of butyraldehyde and diaminopropanol-2.

8. A rubber product which has been vulcanized in the presence of analdehyde derivative of a primary amino hydroxy propane.

9. A rubber product which has been vulcanized in the presence of analdehyde derivative of a di- (primary amino) hydroxy propane.

10. A rubber product which has been Vulcan ized in the presence of analdehyde derivative of a primary amino dihydroxy propane.

11'. The method of treating rubber which comprises vulcanizing it in thepresence of an aldehyde derivative of an amino hydroxy propane in whichthe amino radicals are selected from the group consisting of primaryamino radicals an secondary aliphatic amino radicals.

12. A rubber product which has been vulcanized in the presence of. analdehyde derivative of an amino hydroxy propane in which the aminoradicals are selected from the group consisting of primary aminoradicals and secondary aliphatic amino radicals.

13. A rubber product which has been vulcanized in the presence of thereaction product of an aliphatic aldehyde and a primary amino hydroxypropane.

14. A rubber product which has been vulcanized in the presence of thereaction product of an aromatic aldehyde and a primary amino hydroxypropane.

15. A rubber product which has been vulcanized in the presence of thereaction product of butyraldehyde and l-arnino-Z, 3-dihydroxy propane.

16. A rubber product which has been vulcanized in the presence of thereaction product of butyraldehyde and diamino propanol-2.

JOY G. LICHTY.

